Lithium Iron Disulfide Battery

ABSTRACT

A lithium-iron disulfide battery with improved high temperature performance is disclosed. The separator characteristics are deliberately selected to be compatible with the electrolyte at the intended temperature. Additional or alternative modifications can be made in the form of a scaffold or laminated structure. A preferred polymer for such separators is polyimide.

FIELD OF the INVENTION

The present invention relates to a lithium iron disulfide battery. Inparticular, certain improvements to the polymeric separator andelectrolyte formulation are described.

BACKGROUND OF the INVENTION

Electrochemical cells are presently the preferred method of providingcost effective portable power for a wide variety of consumer devices.The consumer device market dictates that only a handful of standardizedcell sizes (e.g., AA, AAA or AAAA) and specific nominal voltages (e.g.,1.5 V) be provided, while more and more consumer electronic devices,such as digital still cameras, are being designed with relatively highpower operating requirements. Despite these constraints, consumers oftenprefer and opt to use primary batteries for their convenience,reliability, sustained shelf life and more economical per unit price ascompared to currently available rechargeable (i.e., secondary)batteries.

Within this context, it is readily apparent that design choices forprimary non-rechargeable) battery manufacturers are extremely limited.For example, specified, nominal voltages for standard consumer productssignificantly limits the selection of potential electrochemicalmaterials in batteries, while the use of standard cell sizes restrictsthe overall available internal volume available for active materials,safety devices and other elements. Taken together, these choices havemade 1.5 V primary battery systems, such as alkaline or lithium-irondisulfide systems, far more prominent than others, such as 3.0 V andhigher lithium-manganese dioxide.

However, considerations in designing 1.5V primary batteries aresignificantly different are considerably different than higher voltageand/or rechargeable systems. For example, some battery chemistries(e.g., alkaline and nickel oxy-hydroxide) rely on an aqueous and highlycaustic electrolyte that has a propensity for gas expansion and/orleakage, leading to designs, in terms of selection of internal materialsand/or compatibility with containers and closures, that are verydifferent than other chemistries (e.g., lithium-iron disulfide).Further, in rechargeable 1.5 V systems (note that lithium-iron disulfidesystems are not currently considered suitable for consumer-basedrechargeable systems), highly specialized electrochemical compositionsare used, although these high cost components are deemed acceptablebecause secondary systems typically sell for a higher retail price thantheir primary battery equivalents. Additionally, the dischargemechanisms, cell designs and safety considerations of rechargeablesystems are, by and large, inconsequential and/or inapplicable toprimary systems.

Within the realm of 1.5 V systems, lithium-iron disulfide batteries(also referred to as LiFeS₂, lithium pyrite or lithium iron pyrite)offer higher energy density, especially at high drain rates, as comparedto alkaline, carbon zinc or other 1.5 V battery chemistries. But evenwith the inherent advantages of lithium-iron disulfide cells for highpower devices, LiFeS₂ cell designs must strike a balance between thecost of materials used, the incorporation of necessary safety devicesand the overall reliability, delivered capacity and expected conditionsfor use of the cell (e.g., temperature, drain rate, etc.). Normally, lowpower designs emphasize the quantity of active materials, while highpower designs focus more on configurations to enhance dischargeefficiency. As an added consideration, iron-disulfide's propensity toexpand significantly during discharge, in comparison to other batteries,coupled with its relatively hard and granular nature in slurry- and/orroll-coated electrodes, puts extreme stresses on the separator and othercell components during discharge which, if the compromised, could causethe cell to fail to deliver its designed capacity.

Safety devices, such as venting mechanisms and thermally activated“shutdown” elements, and improvements in discharge reliability (e.g., bypreventing internal short circuits) occupy internal cell volume andinvolve design considerations that are usually counterproductive to cellinternal resistance, efficiency and discharge capacity. An additionalchallenge is presented by transportation regulations, which limit theamount of weight lithium batteries can lose during thermalcycling—meaning that cell designs for smaller container sizes like AAand AAA can only lose milligrams of total cell weight (usually by way ofevaporation of the electrolyte). Lastly, the reactive and volatilenature of the non-aqueous, organic electrolytes required for LiFeS₂cells severely limits the universe of potential materials available(particularly with respect to interactions between the electrolyte andcell closure, separator and/or current collector(s) provided within thecell) as compared to other electrochemical systems.

With these considerations in mind, a lithium-iron disulfide battery isdesired which will reliably deliver its fully designed dischargecapacity at temperatures exceeding 70° C. is desired.

BRIEF DESCRIPTION OF the DRAWINGS

The invention will be better understood and other features andadvantages will become apparent by reading the Detailed Description ofthe Invention, taken together with the drawings, wherein:

FIG. 1 is a cross-sectional elevational view of one embodiment of anelectrochemical cell of the present invention. Note that the liquidelectrolyte itself is not shown. Typically much, and in some cases most,of the electrolyte is absorbed into the structures of one or bothelectrodes and the separator material. In addition, there may be anexcess pool of electrolyte at the bottom of cell.

FIGS. 2A-2D illustrate the discharge performance of various separatorcombinations, with FIG. 2A specifically illustrating the prematurevoltage dropoff problem in prior art cells that is specificallyaddressed and solved by certain embodiments of the invention. To furtherclarify, premature voltage dropoff occurs when the discharge voltage fora cell discharged under appropriate conditions drops (and without anysubsequent recovery in intermittent test regimes) and is coupled with adiscernible, concurrent exothermic event within the cell. Usually, thevoltage drop is unexpected (in comparison to the rated cell capacityand/or depth of discharge) and often approaches or drops below thecutoff voltage for the test at issue. In the same manner, the exothermicevent may be observed on the exterior of the cell housing and typicallyappears as a deviation from the observed temperature trend exhibited bythe cell up until that point in the test. Alternatively, in a set ofidentically constructed cells, premature voltage dropoff might beindicated when the discharge capacity delivered by the cells dischargedunder identical conditions varies by more than 10% between cells withinthe set.

FIG. 3 plots the melting point of polyethylene (PE) and polypropylene(PP) separators in selected solvents having differing solubilityparameters.

FIG. 4 correlates the melting point of the polyethylene (PE) separatorsagainst the melting point of polypropylene (PP) separators from FIG. 3.

FIG. 5 is a surface response curve for various sulfolane-basedelectrolytes in lithium-iron disulfide cells discharged at low rate andhigh temperature, as described below.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE INVENTION

The jellyroll electrode assembly is the preferred configuration inLiFeS₂ systems. In order to effectively utilize iron disulfide in thisconfiguration, the iron disulfide is mixed into slurry with the minimalamount of conductors and binders permitted to still effectivelydischarge the cell. This slurry is then coated and dried on a metallicfoil current collector for utilization in the jellyroll, while thelithium is most effectively provided without a current collector. Aseparator is wound between the electrodes, and liquid, non-aqueouselectrolyte is added.

Because the reaction end products of the lithium-iron disulfideelectrochemical reaction occupy substantially more volume than theinputs, the electrode assembly swells as the battery discharges. Inturn, swelling creates radial forces that can cause unwanted bulging ofthe cell container, as well as short circuits if the separator iscompromised. Previous means of handling these problems include usingstrong (often thicker) materials for the cell housing and inactivecomponents within the cell, including the separator. However, thickerinactive materials limit the internal volume available and allow forfewer winds possible in the jellyroll, resulting in less surface areabetween the electrodes and the expectation of comparatively lowerperformance at higher drain rates. Therefore, there is a tension inlithium-iron disulfide cell design to balance the thickness of theseparator against its desired performance and safety characteristics.

In recent years, numerous improved separator materials have beenproposed to improve both the performance and safety of electrochemicalcells. However, these materials have been almost exclusively focused onrechargeable systems, where traits such as cycling characteristics andelectrolyte retention are important. For example, most rechargeablesystems have less than 10% electrode expansion and contraction.Additionally, rechargeable systems respond rapidly to a hard internalshort, which places an emphasis on the ability of the separator toprevent runaway reactions that are not endemic to the lithium-irondisulfide primary battery chemistry.

In comparison, relatively little effort has been made to create alithium-iron disulfide cell design and separator which better utilizesand optimizes the advantages inherent to this primary battery system.For example, lithium-iron disulfide cells may generate in excess of 1500psi of force during discharge (i.e., an amount that is greater than the10% electrode expansion experienced by rechargeable cells), which ismuch greater than many rechargeable systems To further elucidate thispoint, United States Patent Publication No. 2009/0104520 is incorporatedby reference herein.

The hardness of pyrite presents relatively unique puncture concerns, interms of separator strength. Because the lithium-iron disulfide systemreacts to internal shorts slowly (as compared to rechargeable systems)and in such a manner that is control and limit heat generation, aseparator which simply by slows or hinders the ionic flow within thecell can be used without requiring as rapid of a shutdown mechanism asin rechargeable cells.

In view of the foregoing, a primary, lithium-iron disulfide batteryspecifically designed to optimize the advantages and requirements ofthis electrochemical system is contemplated. The inventors havediscovered the interplay of the separator and electrolyte is such that,at extremely high temperatures (typically, temperatures at or exceedingat least 60° C., 71° C. and, in the most extreme case, 90° C.),polypropylene and/or polyethylene microporous membranes no longerprovide consistent, reliable discharge service. Accordingly,improvements to each of these elements, as described herein, enable alithium-iron disulfide battery with improved reliability, dischargecapability at extremely high temperatures (as defined above) and overallenhanced safety owing to the elimination of unwanted short circuits thatmay develop at extremely high temperature, particularly duringintermittent, low rate discharge conditions (typically, at or less than0.10 C, 0.05 C or 0.01 C with discharging intermittently so that thedischarge occurs 50% or less of the total time of the test).

In particular, the inventors determined the failure mode at extremelytemperature and intermittent, low discharge rates (as defined above) wassoftening of the separator due to electrolyte absorption at elevatedtemperature, which can lead to separator penetration by cathodeparticles due to expansion during discharge. Key evidence used toidentify this failure mode is an exothermic response (temperature spikedue to formation of a high-resistance internal short) which closelyaligns with abruptly dropping cell voltage.

In effect, the inventive cell design balances the tensile strength ofthe separator, taking into account the effects of temperature andelectrolyte solubility, against the pore distribution necessary tosustain acceptable performance of the final battery. Accordingly, anycombination of the following elements can be incorporated into a celldesign in order to improve and sustain the discharge performance at orabove 90° C. of spirally wound lithium-iron disulfide cells

-   -   a. Non-woven polymeric separators, preferably comprising        polyimide, are coupled to a microporous polyolefin separator,        preferably comprising polyethylene and/or polypropylene,        particularly at 0.01 C, 50% intermittent discharge at 90° C.    -   b. A liquid electrolyte solution including 20-40 wt % sulfolime.        Alternatively, any solvent which displays a high solubility        parameter (e.g., at least 25 (J/cm³)^(1/2) may provide        sufficient resilience with respect to the polymeric separator to        prevent softening, degradation and/or failure of the separator        at the required temperatures.    -   c. A separator comprising a high temperature polymeric scaffold        (i.e., formed with apertures creating voids which penetrate        completely through the plane of the separator and occupy at        least 50% of the volume occupied by the separator structure),        preferably comprising polyimide, coupled with a second separator        polymeric material that is soluble or highly absorptive of/in        the electrolyte composition and retained in apertures of the        scaffold (either thru atomic or molecular bonding, adhesion,        ionizing radiation or other cross-linking techniques), to create        a two-phase structure having appropriate mechanical and thermal        properties wherein the second material forms a continuous,        pore-filling phase that provides ionic conductivity and        preferably (but optionally) swells when positioned within the        aperture.    -   d. An “asymmetric” separator with multiple, discrete layers        having: i) pore sizes in each layer varying so that the across        the total thickness and ii) compositions with differing melting        points varying in each layer, creating a micro/macro-pore        combination that enhances thermal shutdown (with respect to the        former) and providing good mechanical strength at extremely high        temperatures (with respect to the later). At least one of the        layers can be impregnated (i.e., the pores may be filled) to        further enhance ionic conductivity. Preferably, the lower        melting point material possesses comparatively smaller pores        (relative to the other layer(s)/material(s)) to facilitate the        desired thermal shutdown. An optional third layer, preferably        identical to one of the others, could be used to create a        sandwiched separator structure that allows for more easy        impregnation and/or handling of the separator.

An exemplar embodiment of an electrochemical cell design appropriate forthe components identified above is illustrated in FIG. 1. Cell 10 is aprimary FR6 type cylindrical Li/FeS₂ cell. However, it is to beunderstood that, as described herein, the invention is applicable toother cell types, materials, and constructions, and the descriptionregarding FR6 cells is not intended to be limiting. For example,bobbin-style, prismatic and coin cell constructions, utilizing variousknown battery chemistries, are or may be amenable to embodiments of theinvention.

With reference to FIG. 1, Cell 10 has a housing that includes acontainer in the form of a can 12 with a closed bottom and an open topend that is closed with a cell cover 14 and a gasket 16. The can 12 hasa bead or reduced diameter step near the top end to support the gasket16 and cover 14. The gasket 16 is compressed between the can 12 and thecover 14 to seal an anode or negative electrode 18, a cathode orpositive electrode 20 and electrolyte within the cell 10. The anode 18,cathode 20 and a separator 26 are spirally wound together into anelectrode assembly. The cathode 20 has a metal current collector 22,which extends from the top end of the electrode assembly and isconnected to the inner surface of the cover 14 with a contact spring 24.The anode 18 is electrically connected to the inner surface of the can12 by a current collector such as a tab or metal lead 36. The lead 36 isfastened to the anode 18, extends from the bottom of the electrodeassembly and is folded across the bottom and up along the side of theelectrode assembly in one embodiment. The lead 36 may be welded, or makepressure contact with the inner surface of the side wail of the can 12as shown. After the electrode assembly is wound, it can be held togetherbefore insertion by tooling in the manufacturing process, or the outerend of material (e.g., separator or polymer film outer wrap 38) can befastened down, by heat sealing, gluing or taping, for example.

An insulating cone 46 can be located around the peripheral portion ofthe top of the electrode assembly to prevent the cathode currentcollector 22 from making contact with the can 12, and contact betweenthe bottom edge of the cathode 20 and the bottom of the can 12 isprevented by the inward-folded extension of the separator 26 and anelectrically insulating bottom disc 44 positioned in the bottom of can12.

Cell 10 has a separate positive terminal cover 40, which is held inplace by the inwardly crimped top edge of the can 12 and the gasket 16and has one or more vent apertures (not shown). The can 12 serves as thenegative contact terminal. An insulating jacket, such as an adhesivelabel 48, can be applied to the side wall of the can 12.

Separator

When nonaqueous electrolytes are used, a separator membrane that ision-permeable and electrically nonconductive should possess at least oneof the characteristics identified above. The separator should be capableof retaining at least some electrolyte within the pores of theseparator. The separator is disposed between adjacent surfaces of theanode and cathode to electrically insulate the electrodes from eachother. Portions of the separator may also insulate other components inelectrical contact with the cell terminals to prevent internal shortcircuits. Edges of the separator often extend beyond the edges of atleast one electrode to insure that the anode and cathode do not makeelectrical contact even if they are not perfectly aligned with eachother. However, it is desirable to minimize the amount of separatorextending beyond the electrodes.

Suitable separator materials should also be strong enough to withstandcell manufacturing processes as well as pressure that may be exerted onthe separator during cell discharge without tears, splits, holes orother gaps developing that could result in an internal short circuit. Tominimize the total separator volume in the cell, the separator should beas thin as possible, preferably less than 50 μm thick, and morepreferably no more than 25 μm thick, and most preferably as thin as 20μm or 16 μm. A high tensile stress is desirable, preferably at least800, more preferably at least 1000, kilograms of force per squarecentimeter (kgf/cm²). Preferably the average dielectric breakdownvoltage exceeds 1000 volts, 2000 volts or most preferably 2400 volts.Preferably the area specific resistance of the electrolyte-separatorcombination (i.e., measured as a function of the electrolyte selectedfor the battery) is no greater than 15 ohm-cm², more preferably nogreater than 4.0 ohm-cm², and most preferably no greater than 2.0ohm-cm². Preferably, the mix penetration strength of the separator whenimmersed in the electrolyte composition intended for the final celldesign and heated to at least 60° C. should be greater than 800 psi andmore preferably greater than 1000 psi.

During long-term (low rate) discharge, the separator experiences highstress for an extended period in lithium-iron disulfide cells. Thispressure can lead to cathode particles penetrating the separator,internally shorting the cell. The rigidity, shape, and upper particlesize limit of the cathode particles further exacerbate this concern.Penetration of the separator is a potential cause of imperfect low ratereliability, especially in spirally wound AA and AAA battery sizes,thereby causing cells to exhibit premature voltage dropoff (or PVD, asdefined above), wherein the cell voltage drops suddenly and unexpectedlyat greater than 50% depth of discharge and is concurrently associatedwith a rise in cell temperature (above the ambient dischargetemperature), at extremely high temperature (i.e., at least 70° C.). Inturn, PVD limits battery reliability and can be directly attributed toseparator performance. Moreover, selection of electrolyte may softencertain polymeric materials and further exacerbate PVD issues atextremely high temperatures.

Although current microporous separators for nonaqueous cells are almostexclusively polyethylene (PE) and/or polypropylene (PP), the inventorshave identified other polymers with improved stability and mechanicalstrength at high temperatures in the lithium-iron disulfide system.Specifically, polymers should have either high melting point (>200° C.)or display little or no compromise in mechanical strength at hightemperature (>150° C.). Separators composed of such polymers may solvethe PVD problem encountered during low rate discharge at temperaturesabove 60° C., and more preferably at or above 90° C.

Among these specialty separators, polyimide (PI) nonwoven separator wasselected because of the excellent thermal stability of PI. The basicproperties of this PI separator are compared to those of a typical 20 umPE separator used in current prior art batteries (see Table 1). It isdear that the nonwoven PI separator is thermally more stable than themicroporous PE separator, but it is more porous and has much larger poresize and lower tensile strength because these two types of separators,made by using different processes, have completely different structures.

TABLE 1 Comparison of properties of nonwoven PI separator andmicroporous PE separator Properties Nonwoven PI Micro-porous PEThickness (um) 22-23 20 Porosity    50-66% 36-46% Avg. pore size (um) ~1<0.1 Melting point (° C.) N/A ~135 Degradation temperature:    >400° C.Tensile Strength in MD (kg/cm2) 440 760

Notwithstanding the desirable properties of nonwoven PI separators,testing demonstrated that PI alone did not solve the PVD problem. Thedirect cause of lower-than-expected service for the nonwoven PIseparator was attributed to large pore size and insufficient thickness.To overcome these deficiencies, the PI separator (or a similar non-wovenpolymeric separator possessing a majority of the same characteristics ofPI identified in table 1 above) is used in combination with a thinnerversion of a standard microporous separator (e.g., a polyethylene orpolypropylene separator similar to those currently in use incommercially available lithium-iron disulfide cells). The two separatorscan be wound together or bound (e.g., adhesively or chemically) duringthe regular manufacturing process. The resulting bi-layer separatorprovides the desired high temperature and drain rate performance.

With respect to bi-layer separators made of nonwoven PI and microporousPE, the overall increase separator thickness necessitated the use ofmuch shorter, thicker electrodes to maintain comparable theoretical,interfacial input capacities in comparison to prior art cells using onlythe thinner PE separator. The PI layer can be 20 microns, 25 microns, 30microns, 40 microns or any value therebetween, while the PE layer ispreferably 10 microns, 15 microns, 20 microns, 25 microns or any valuetherebetween. The resulting bi-layer should be between 30 and 75microns, with the preferred value being between 35 to 40 microns.

For bi-layer separator constructions using PI-PE separators, twodifferent PI-PE orientations were evaluated: PI adjacent to the cathodeand PI adjacent to the anode. Discharge curves in FIGS. 2(A) through2(D) show that the control (single layer of 20 μm PE) had severe PVDwhereas both lots with bi-layer separators of PE-PI (regardless of theorientation of the PI layer) delivered the expected discharge capacitywithout any PVD on 20 mA discharge at 90° C. Conversely, even the“reference” cell using a double layer of PE-PE and electrodes of similarlength and thickness to the bi-layer separators still showed PVD.

Additionally, other materials may be used as a scaffold material incombination with a second polymeric filler, as described above. In thesecases, the scaffold polymer should have a high melting temperature(e.g., >140° C.), be resistant to chain scission when exposed toionizing radiation and be insoluble in the selected electrolytecomposition and non-reactive with the electrode materials. Potentialscaffold materials include polyimide, polyester, polyamide,poly(phthalamide) and/or poly(vinyl choloride). The second pore fillingpolymer should readily absorb and/or dissolve in the selectedelectrolyte composition, crosslink upon exposure to ionizing radiationand be caopable of solution casting, melt processing or other processesthat introduce the polymer into the interstices/pores of the scaffoldmaterial. Potential second polymer materials include poly(vinylidenefluoride), polyacrylate and polyethylene copolymers (such as EVA, EAA,etc.).

Laminate materials consistent with the assymetric separator conceptdescribed above might include PP, PE, PET, polyester, polyimide,polyamide and other polymers capable of being formed into pores filmsand/or possessing a higher melting point than microporous PE or PP whichwould form one of the layered bases in this embodiment. The materialscould be laminated, coated or impregnated.

Suitable separators and/or materials having the properties describedabove may be available from, inter alia, Tonen Chemical Corp. inKawasaki-shi Japan, Entek Membranes in Lebanon, Oreg., USA; and/orDupont Chemical Corporation in Circleville, Ohio, USA.

Electrolyte Composition

Irrespective of the cell construction, the electrolyte composition(which typical consists of at least one solute dissolved in at least oneorganic liquid solvent) has several characteristics. Foremost, it mustbe compatible with the components of the positive and negativeelectrodes in order to facilitate the desired electrochemical reactions.Additionally, it must not degrade or react with any internal componentsof the cell itself.

Absent actual experimentation, it is generally not known how aparticular additive dissolved in an electrolyte will behave or reactafter exposure to and storage in a particular electrochemical cellsystem. For example, the additive should be stable to both the anode(reductant) and cathode (oxidant), usually for many years and must notsubstantially diminish cell functionality or additive efficacy.Moreover, strong interactions between components of cells—especiallythose between the electrolyte and electrode surfaces—often involvecomplex chemistry that is poorly understood. Thus, electrolytes are ahighly unpredictable art, and one cannot generally predict the utilityof additives in a particular system in the absence of specific celltesting.

The nonaqueous electrolyte composition in one embodiment of the presentinvention, contains water only in very small quantities (e.g., no morethan about 2,000, or more preferably no more than 500, parts per millionby weight, depending on the electrolyte salt being used). Any nonaqueouselectrolyte suitable for use with lithium and active cathode materialmay be used. The electrolyte contains one or more solutes, e.g.electrolyte salts dissolved in an organic solvent. Because theelectrolyte is the primary media for ionic transfer in a Li/FeS₂ cell,selection of an appropriate solvent and solute combination is criticalto optimizing the performance of the cell. Moreover, the solute andsolvents selected for the electrolyte must possess appropriatemiscibility and viscosity for the purposes of manufacture and use of theresulting cell, while still delivering appropriate discharge performanceacross the entire spectrum of temperatures potentially experienced bybatteries (i.e., about −40° C. to 90° C.).

Miscibility and viscosity of the solvents and the electrolyte is key tothe manufacturing and operational aspects of the battery. All solventsused in the blend must be completely miscible to insure a homogeneoussolution. Similarly, in order to facilitate high volume production, thesolvents should be liquid during manufacture and discharge of the celland ideally possess a sufficiently low viscosity to flow and/or bedispensed quickly.

Additionally, the solvents and the electrolyte must possess a boilingpoint appropriate to the temperature range in which the battery willmost likely be exposed and stored (e.g., −60° C. to greater than 100°C.). More specifically, the solvent(s) must be sufficiently non-volatileto allow for safe storage and operation of the battery within thisstated temperature range. Similarly, the solvents and the electrolytemust not react with the electrode materials in a manner that degradesthe electrodes or adversely affects performance of the battery upondischarge.

Suitable organic solvents that have been or may be used in Li/FeS₂ cellshave included one or more of the following: 1,3-dioxolane; 1,3-dioxolanebased ethers (e.g., alkyl- and alkoxy-substituted DIOX, such as2-methyl-1,3-dioxolane or 4-methyl-1,3-dioxolane, etc.);1,2-dimethoxyethane; 1,2-dimethoxyethane-based ethers (e.g., diglyme(DG), triglyme (TrG), tetraglyme, ethyl glyme, etc.): ethylenecarbonate; propylene carbonate (PC); 1,2-butylene carbonate;2,3-butylene carbonate; vinylene carbonate; dimethyl carbonate (DMC);diethyl carbonate; ethyl methyl carbonate; methyl formate;γ-butyrolactone; sulfolane (SULF); acetonitrile; N,N-dimethyl formamide:N,N-dimethylacetamide; N,N-dimethylpropyleneurea;1,1,3,3-tetramethylurea; beta aminoenones; beta aminoketones;methyltetrahydrofurfuryl ether; diethyl ether; tetrahydrofuran (THF);2-methyl tetrahydrofuran; 2-methoxytetrahydrofuran;2,5-dimethoxytetrahydrofuran; 3-methyl-2-oxazolidinone;3,5-dimethylisoxazole (“DMI”); 1-ethoxy-2-methoxypropane;1,2-dimethoxypropane; and 1,2-dimethoxypropane-based compounds.Additionally, other solvents may act as additives to impart furthercharacteristics upon a particular electrolyte; for example, smallamounts of pyridine, triethylamine or other organic bases may be used tocontrol polymerization of the solvent(s). For cells requiring aqueouselectrolytes, any number of solutions containing hydroxide (preferablypotassium, sodium or lithium hydroxide(s) and the like), chloride(preferably ammonium or zinc chloride and the like) or acid (preferablysulfuric and the like), may be employed.

Salts should be nearly or completely soluble with the selectedsolvent(s) and, as with the discussion of solvent characteristics above,without any degradation or adverse effects. Examples of typical saltsused in Li/FeS₂ cells include LiI (“lithium iodide”), LiCF₃SO₃ (“lithiumtrifluoromethanesulfonate or lithium triflate”). LiClO₄ (“lithiumperchlorate”), Li(CF₃SO₂)₂N (“lithium bis(trifluorosulfonyl)imide orlithium imide”), Li(CF₃CF₂SO₂)₂N and Li(CF₃SO₂)₃C. Other potentialcandidates are lithium bis(oxalato)borate, lithium bromide, lithiumhexafluorophosphate, and lithium hexafluoroarsenate. Potassium analogsof these salts may also be used, as a partial or complete replacementfor their lithium analogs. Two key aspects of salt selection are thatthey do not react with the housing, electrodes, sealing materials orsolvents and that they do not degrade or precipitate out of theelectrolyte under the typically expected conditions to which the batterywill be exposed and expected to operate (e.g., temperature, electricalload, etc.). It is possible to use more than one solute to maximizecertain aspects of performance.

Notably, unless noted to the contrary, the concentration of the solutesrelative to the solvents as described herein is best expressed as molesof solute per kilogram of solvent (molality). Molality of a solutionremains constant irrespective of the physical conditions liketemperature and pressure, whereas the volume of some solvents typicallyincreases with in temperature thereby yielding a decrease in molarity(i.e., moles per liter solution), although this effect is usually small.

Lithium iodide is the preferred solute for primary nonaqueous cells witha cell voltage below 2.8V, although other solutes provided to thissolvent blend would be expected to exhibit similar benefits (includingbut not limited to lithium perchlorate, lithium triflate, lithium imideand the like). The preferred solute concentration is about 0.75 molal.

The inventors have observed that the melting points (MP), especially ofcommon polymers used for making microporous separators such as PE andPP, are around 135° C. and 165° C., respectively. In turn, the thermalshutdown temperature of such separators, which corresponds to the MP ofthe polymer separator inside the cell, was substantially lower than thatof the polymer separator by itself. The interactions between thesolvents and polymer could reduce the mechanical strength, soften thepolymer matrix, and allow the polymer chains to move more easily underpressure, especially at elevated temperatures. Therefore, through theselection of solvents or solvent blends that interact minimally with PEor PP, PVD may be solved without the need of specialty polymers or verythick PE and PP separators.

Interactions between the polymer and solvents can be quantified usingthe solubility parameter (δ), which has been defined as the square rootof the cohesive energy density and describes the attractive strengthbetween molecules of the material. Materials with similar solubilityparameters are likely to be miscible when determined for the samecategory of hydrogen bonding. When strong hydrogen bonding is present,it is more appropriate the use the following equation for assessing themiscibility of the two organic materials:

δ=δ_(D) ²+δ_(P) ²+δ_(H) ²

where δ_(D), δ_(P), and δ_(H) account for contributions from dispersion,polar, and hydrogen-bonding interactions, respectively. Miscibility ispredicted to be most probable when δ_(D,1)≈δ_(D,2), δ_(P,1)≈δ_(P,2), andδ_(H,1)≈δ_(H,2). In this case, no significant hydrogen-bondinginteraction is expected. Thus, the individual components of thesolubility parameter (δ) need not be known.

To reduce the swelling of polymers, such as PE and PP, by the solventsat elevated temperatures, the nonaqueous solvents with solubilityparameters much higher than that of polymer of the separator aredesired. In general, these solvents are polar solvents and/or solventswith boiling point (BP) higher than 85° C. may help overcome the PVDissues at extremely high temperatures. In addition, the use of thesehigh BP solvent should reduce weight loss on thermal cycling tests.Representative solvents are identified in Table 3.

TABLE 3 Solubility parameter, melting point (MP), and boiling point (BP)of solvents evaluated for this project Solubility parameters MP BPSolvent # Abbreviation Solvents (J/cm³)^(1/2) (° C.) (° C.) 1 DME1,2-Dimethoxyethane 17.7 −58 84.5 2 DIOX 2,3-Dioxolane 17.6 −97.22 76.53 DG Diglyme, bis(2-methoxethyl) 19.2 −64 163 ether 4 TrG Triglyme,1,2-bis(2- ? −45 216 methoxyethoxy)ethane 5 THF Tetrahydrofuran 18.6−108.5 66 6 CME Cyclopentyl methyl ether 106 7 MTHFFEMethyltetrahydrofurfuryl ether 140 8 DMC Dimethylcarbonate 20.3 4.8 90 9PC Propylene carbonate 27.2 −54.5 242 10 DMMP Dimethyl methylphosphonate181 11 TEP Triethyl phosphonate −56 215 12 DEEP Diethyl ethylphosphonateN/A N/A 13 3Me2Ox 3-Methyl-2-oxazolidane 15.9 88-90/1 mmHg 14 EMS Ethylmethyl sulfone 27.4 32-37 N/A 15 DMS Dimethyl sulfone 29.9 109 238 16SULF Tetramethylene sulfone 27.4 27 285 17 3MSL 3-Methylsulfolane N/A267

Thus, the inventors have found that the melting point of the polymer ofthe separator in the presence of a solvent can be a convenient and goodindex for assessing of the interactions between the solvent and theseparator. All MP measurements were carried out on a TA differentialscanning calorimeter (DSC): model Q2000 at a rate of 10° C./min fromroom temperature to 220° C., although special equipment may be needed tosustain sufficient pressure for measuring the MP of some polymers in thepresence of solvents at temperatures approaching or above their MP.

As an example of this technique, Table 4 shows that while DME, DIOX, andtheir blends significantly lower the MP of the PE and PP, there are manyother solvents that have essentially no effect on the MP of the PE andPP. The addition of the LiI salt had minor effect on increasing the MPof the PE and PP when compared to solvent blend only (an increase of 5°C. for both PE and PP). As expected, the MP of PE and PP separatorsincreased with increasing solubility parameter as shown in FIG. 3.

TABLE 4 MP of PE and PP separator immersed in various solventsSolvent/Electrolyte PE MP (° C.) PP MP (° C.) 65% DIOX:35% DME blend 119130 (v/v) DIOX 121 127 DME 122 130 0.75m Lil in 124 135 65% DIOX:35% DMEblend (v/v) 60% DIOX, 70% DG 128 139 DG 130 146 DMC 130 147 30% DME:70%PC (v/v) 134 156 DEEP 135 154 TEP 137 160 DMMP 138 161 PC 139 165 3Me2Ox139 164 EMS 140 165 SULF 140 166 Ref. (no solvent) 137 167

For a solvent with a given solubility parameter, reduction of themelting point of PP is double the reduction of the melting point of PEas seen in FIG. 4. Thus, although the MP of dry PP is ˜40° C. higherthan that of dry PE, it is only ˜10° C. higher in the presence of theall-ether electrolytes used in known lithium-iron disulfide cells. ThisMP may also serve as a proxy for other significant separator traits,such as puncture resistance and mechanical strength.

To maximize MP, electrolyte blends that contain a very large percentage,up to 100%, of the solvents with high solubility parameter are desired.However, these solvents are polar, have higher viscosity, and tend toreact more with the lithium anode. Thus, these solvents or solventblends may have very poor performance on high rate at both room and lowtemperatures. In other words, there are likely trade-offs in theperformance between low rate at high temperature (e.g. 90° C.) and highrate at room and low temperatures when using solvents with highsolubility parameters. Therefore, a wide range of the solventcompositions muts be explored to understand these trade-offs after theidentification of the promising solvents through the screeningexperiments.

On the 20 mA discharge at 90° C., sulfolane (SULF) was a solventidentified as having a positive effect on improving the reliability ofthe performance. When incorporated into lithium-iron disulfide cellsdischarged at intermittent, low rate and extremely high temperature,none of the SULF electrolyte compositions experienced significant PVD,as further illustrated in Table 5. In turn, the surface response of theSULF electrolyte compositions is illustrated in FIG. 5, where Arepresents a 1,2-dimethoxyethane component, B represents a sulfolanecomponent and C represents a 1,3-dioloxane component.

TABLE 5 Cell Performance with SULF-containing electrolytes Avg. service#PVD <90% Avg. service on Stdev for on on Li imide 20 mA/90° C. 20mA/90° C. 20 mA/90° C. 1000 mA/21° C. DIOX (vol %) DME (vol %) Sulfolane(vol %) concentration (mAh) (mAh) test (mAh) 30% 20% 50% 0.6 m 2831 220/4 2624 0% 30% 70% 0.6 m 2828 53 0/4 2225 25% 10% 65% 0.6 m 2955 70 0/42285 15% 15% 70% 0.6 m 2846 83 0/4 2069 15% 30% 55% 0.6 m 2941 86 0/42561 25% 25% 50% 0.6 m 2890 38 0/4 2675 30% 30% 40% 0.6 m 2868 75 0/42712 20% 20% 60% 0.6 m 2865 22 0/4 2413 30% 15% 55% 0.6 m 2879 57 0/42553 10% 30% 60% 0.6 m 2939 75 0/4 2564 30% 0% 70% 0.6 m 2925 83 0/41907 20% 20% 60% 0.6 m 2893 87 0/4 2541 40% 40% 20% 0.6 m 2841 95 0/42752 80% 0% 20% 0.6 m 2833 42 0/4 2322

At least 20 vol % SULF is required to remain essentially free of PVD at≦85% DOD. Although mild shorting was detected in both the control lotand 40 vol % SULF lot, none of the cells tested failed at ≦85% DOD thatused SULF-containing electrolyte. In addition to SULF, its derivative3-methylsulfolane (3MSL) also performed well; however, 3MSL is much moreexpensive than SULF and does not offer any other advantage on high rateperformance, investigation of 3MSL will be discontinued.

Other Cell Components

The cell container is often a metal can with a closed bottom such as thecan in FIG. 1. The can material will depend in part of the activematerials and electrolyte used in the cell. A common material type issteel. For example, the can may be made of steel, plated with nickel onat least the outside to protect the outside of the can from corrosion.The type of plating can be varied to provide varying degrees ofcorrosion resistance or to provide the desired appearance. The type ofsteel will depend in part on the manner in which the container isformed. For drawn cans the steel can be a diffusion annealed, lowcarbon, aluminum killed, SAE 1006 or equivalent steel, with a grain sizeof ASTM 9 to 11 and equiaxed to slightly elongated grain shape. Othersteels, such as stainless steels, can be used to meet special needs. Forexample, when the can is in electrical contact with the cathode, astainless steel may be used for improved resistance to corrosion by thecathode and electrolyte.

The cell cover can be metal. Nickel plated steel may be used, but astainless steel is often desirable, especially when the cover is inelectrical contact with the cathode. The complexity of the cover shapewill also be a factor in material selection. The cell cover may have asimple shape, such as a thick, flat disk, or it may have a more complexshape, such as the cover shown in FIG. 1. When the cover has a complexshape like that in FIG. 1, a type 304 soft annealed stainless steel withASTM 8-9 grain size may be used, to provide the desired corrosionresistance and ease of metal forming. Formed covers may also be plated,with nickel for example.

The terminal cover should have good resistance to corrosion by water inthe ambient environment, good electrical conductivity and, when visibleon consumer batteries, an attractive appearance. Terminal covers areoften made from nickel plated cold rolled steel or steel that is nickelplated after the covers are formed. Where terminals are located overpressure relief vents, the terminal covers generally have one or moreholes to facilitate cell venting.

The gasket is made from any suitable thermoplastic material thatprovides the desired sealing properties. Material selection is based inpart on the electrolyte composition. Examples of suitable materialsinclude polypropylene, polyphenylene sulfide,tetrafluoride-perfluoroalkyl vinylether copolymer, polybutyleneterephthalate and combinations thereof. Preferred gasket materialsinclude polypropylene (e.g., PRO-FAX® 6524 from Basell Polyolefins inWilmington, Del., USA) and polyphenylene sulfide (e.g., XTEL™ XE3035 orXE5030 from Chevron Phillips in The Woodlands, Tex., USA). Small amountsof other polymers, reinforcing inorganic fillers and/or organiccompounds may also be added to the base resin of the gasket.

The gasket may be coated with a sealant to provide the best seal.Ethylene propylene diene terpolymer (EPDM) is a suitable sealantmaterial, but other suitable materials can be used.

If a ball vent is used, the vent hushing is made from a thermoplasticmaterial that is resistant to cold flow at high temperatures (e.g., 75°C.). The thermoplastic material comprises a base resin such asethylene-tetrafluoroethylene, polybutylene terephthlate, polyphenylenesulfide, polyphthalamide, ethylene-chlorotrifluoroethylene,chlorotrifluoroethylene, perfluoro-alkoxyalkane, fluorinatedperfluoroethylene polypropylene and polyetherether ketone.Ethylene-tetrafluoroethylene copolymer (ETFE), polyphenylene sulfide(PPS), polybutylene terephthalate (PBT) and polyphthalamide arepreferred. The resin can be modified by adding a thermal-stabilizingfiller to provide a vent bushing with the desired sealing and ventingcharacteristics at high temperatures. The bushing can be injectionmolded from the thermoplastic material. TEFZEL® HT2004 (ETFE resin with25 weight percent chopped glass filler), polyphthalamide (e.g., AMODEL®ET 10011 NT, from Solvay Advanced Polymers, Houston, Tex.) andpolyphenylene sulfide (e.g., e.g., XTEL™ XE3035 or XE5030 from ChevronPhillips in The Woodlands, Tex., USA) are preferred thermoplasticbushing materials.

The vent ball itself can be made from any suitable material that isstable in contact with the cell contents and provides the desired cellsealing and venting characteristic. Glasses or metals, such as stainlesssteel, can be used. In the event a foil vent is utilized in place of thevent ball assembly described above (e.g., pursuant to U.S. PatentApplication Publication No. 2005/0244706 herein incorporated byreference), the above referenced materials may still be appropriatelysubstituted.

Any number or combination of the aforementioned components may betreated or provided with a coating so as to impart additional desiredcharacteristics to cell. By way of example rather than limitation, theseal member(s) (e.g., the gasket, vent, cell cover, etc.) may be coatedwith a composition to inhibit the ingress or egress of moisture orelectrolyte solvents therethrough. The interior of the container mayalso be coated to improve cell performance and/or manufacture. To theextent that such coatings or treatments are utilized, it is possible tointroduce the contrast agent into the cell as part of this/thesecoating(s) as an additional or alternative embodiment of the invention,so long as the component containing the contrast agent remains exposedto an internal surface of the cell, thereby allowing dissolution anddispersion of the contrast agent with the electrolyte composition.

Electrodes

The anode comprises a strip of lithium metal, sometimes referred to aslithium foil. The composition of the lithium can vary, though forbattery grade lithium, the purity is always high. The lithium can bealloyed with other metals, such as aluminum, to provide the desired cellelectrical performance or handling ease, although the amount of lithiumin any alloy should nevertheless be maximized. Appropriate battery gradelithium-aluminum foil, containing 0.5 weight percent aluminum, isavailable from Chemetall Foote Corp., Kings Mountain, N.C., USA.

Other anode materials may be possible, including sodium, potassium,zinc, magnesium and aluminum, either as co-anodes, alloying materials ordistinct, singular anodes. Anodes such as carbon, silicon, tin, copperand their alloys, as well as lithium titanate spinel, that have beenreported and in some cases commonly used in lithium-ion and otherprimary or secondary cells can also be used. Ultimately, the selectionof an appropriate anode material will be influenced by the compatibilityof that anode with electrolyte and performance in the cell. The physicalattributes of the alloy may also be important, especially for a spiralwound cell, because the alloy has to have enough flexibility to bewound. The amount that the anode stretches during such winding can alsobe important. Thus, the physical properties of the alloy need to bematched against the processes used to make the cell.

As in the cell in FIG. 1, a separate current collector (i.e., anelectrically conductive member, such as a metal foil, onto which theanode is welded/coated or an electrically conductive strip running alongthe length of the anode) may not needed for the anode, since lithium hasa high electrical conductivity. By not utilizing such a currentcollector, more space is available within the container for othercomponents, such as active materials. Anode current collectors may bemade of copper and/or other appropriate high conductivity metals so aslong as they are stable when exposed to the other interior components ofthe cell (e.g., electrolyte), and therefore also affect cost.Alternatively when the anode is provided in a bobbin-style construction,the current collector may be nail, conductive wire or other similarstructure.

In jellyroll and prismatic constructions, the electrical connectionshould be maintained between each of the electrodes and the opposingterminals proximate to or integrated with the housing. An electricallead 36 can be made from a thin metal strip connecting the anode ornegative electrode to one of the cell terminals (the can in the case ofthe FR6 cell shown in FIG. 1). When the anode includes such a lead, itis oriented substantially along a longitudinal axis of the jellyrollelectrode assembly and extends partially along a width of the anode.This may be accomplished embedding an end of the lead within a portionof the anode or by simply pressing a portion such as an end of the leadonto the surface of the lithium foil. The lithium or lithium alloy hasadhesive properties and generally at least a slight, sufficient pressureor contact between the lead and electrode will weld the componentstogether. The negative electrode may be provided with a lead prior towinding into a jellyroll configuration. The lead may also be connectedvia other appropriate welds.

The metal strip comprising the lead 36 is often made from nickel ornickel plated steel with sufficiently low resistance (e.g., generallyless than 15 mΩ/cm and preferably less than 4.5 mΩ/cm) in order to allowsufficient transfer of electrical current through the lead and haveminimal or no impact on service life of the cell. A preferred materialis 304 stainless steel. Examples of other suitable negative electrodelead materials include, but are not limited to, copper, copper alloys,for example copper alloy 7025 (a copper, nickel alloy comprising about3% nickel, about 0.65% silicon, and about 0.15% magnesium, with thebalance being copper and minor impurities); and copper alloy 110; andstainless steel. Lead materials should be chosen so that the compositionis stable within the electrochemical cell including the electrolyte.

The cathode may be ring molded, provided as a pellet or in the form of astrip that comprises a current collector and a mixture that includes oneor more electrochemically active materials, usually in particulate form.Iron disulfide (FeS₂) is a preferred active material although theinvention is applicable to cathode materials such as MnO₂, FeS, CuO,CuO₂, transition metal polysulfides, nickel oxyhydroxides, oxides ofbismuth (e.g., Bi₂O₃, etc.), and oxides typically used in lithium oncells (i.e., LiFePO₄, LiCoO₂, LiMn_(1/3)Ni_(1/3)Co_(1/3)O₂,Li_(1.1)(Mn_(1/3)Ni_(1/3)Co_(1/3))_(0.9)O₂,LiNi_(0.8)Co_(0.15)Al_(0.05)O₂, LiMn_(1/2)Co_(1/2)O₂, LiMn₂O₄ and thelike). Additionally or alternatively, “doped” materials, comprising anyone or combination of the aforementioned cathode active materials, withsmall amounts of various metals or other materials inserted orchemically bonded into the crystalline structure in order to improve theoverall performance of the resulting cell, may also be used.

In the preferred Li/FeS₂ cell, the active material comprises greaterthan 50 weight percent FeS₂. The cathode can also contain one or moreadditional active materials mentioned above, depending on the desiredcell electrical and discharge characteristics. More preferably theactive material for to Li/FeS₂ cell cathode comprises at least 95 weightpercent FeS₂, yet more preferably at least 99 weight percent FeS₂, andmost preferably FeS₂ is the sole active cathode material. FeS₂ having apurity level of at least 95 weight percent is available from WashingtonMills, North Grafton, Mass., USA; Chemetall GmbH, Vienna, Austria; andKyanite Mining Corp., Dillwyn, Va., USA. A more comprehensivedescription of the cathode, its formulation and a manner ofmanufacturing the cathode is provided below.

The current collector in the preferred cell may be disposed within orimbedded into the cathode surface, or the cathode mixture may be coatedonto one or both sides of a thin metal strip. Aluminum is a commonlyused material. The current collector may extend beyond the portion ofthe cathode containing the cathode mixture. This extending portion ofthe current collector can provide a convenient area for making contactwith the electrical lead connected to the positive terminal. It isdesirable to keep the volume of the extending portion of the currentcollector to a minimum to make as much of the internal volume of thecell available for active materials and electrolyte. Additionally oralternatively, it may be possible to rely upon the conductive qualitiesof the container to act as a current collector.

The cathode is electrically connected to the positive terminal of thecell. This may be accomplished with an electrical lead, often in theform of as thin metal strip or a spring, as shown in FIG. 1, althoughwelded connections are also possible. The lead is often made from nickelplated stainless steel. Still another embodiment may utilize aconnection similar to that disclosed in United States Publication No.2008/0254343, which is commonly assigned to the assignee of thisapplication and incorporated by reference herein. Notably, to the extenta cell design may utilize one of these alternative electricalconnectors/current limiting devices, the use of a PTC may be avoided. Inthe event an optional current limiting device, such as a standard PTC,is utilized as a safety mechanism to prevent runaway discharge/heatingof the cell, a suitable PTC is sold by Tyco Electronics in Menlo Park,Calif., USA. Other alternatives are also available.

The above description is particularly relevant to cylindrical Li/FeS₂cells, such as FR6 and FR03 types, as defined in International StandardsIEC 60086-1 and IEC 60086-2, published by the InternationalElectrotechnical Commission, Geneva, Switzerland. However, the inventionmay also be adapted to other cell sizes and shapes and to cells withother electrode assembly, housing, seal and pressure relief ventdesigns. The electrode assembly configuration can also vary. Forexample, it can have spirally wound electrodes, as described above,folded electrodes, or stacks of strips (e.g., flat plates). The cellshape can also vary, to include cylindrical and prismatic shapes.

Thus, some embodiments of the invention described herein includeelectrochemical cells and batteries, as well as methods formanufacturing and using the same, which have at least one of thefollowing characteristics, although additional characteristics andembodiments and combinations are possible based upon the detailscontained in the disclosure above:

-   -   an anode consisting essentially of lithium or a lithium alloy;    -   a cathode coated onto a solid current collector, said cathode        coating comprising iron disulfide as an active material;    -   a high temperature polymeric separator comprising a polymer        having a melting point;    -   a high temperature polymeric separator having a scaffold        structure comprising a first polymer and filling polymer        comprising a second polymer;    -   an electrolyte having a solubility parameter;    -   a liquid electrolyte that is distinct from the separator;    -   wherein the anode, the cathode and the separator are spirally        wound;    -   wherein, when the cell is discharged at a rate of 0.01 C or less        and a temperature of 70° C. or greater, the solubility parameter        of the electrolyte is large enough relative to the melting point        of the polymer to prevent premature voltage dropoff;    -   wherein the separator comprises polyimide;    -   wherein the separator is a bi-layer further comprising        polyethylene;    -   wherein the polyimide is less than 30 microns, the polyethylene        is greater than 10 microns and a total thickness for the        bi-layer separator is less than 50 microns; and/or    -   wherein the first polymer does not soften at an expected        discharge temperature for the cell.

In accordance with the patent statutes, the scope of the invention isnot limited thereto, but rather by the scope of the attached claims. Theexamples above are merely considered to be specific embodiments of theinvention disclosed herein.

What is claimed:
 1. An electrochemical cell comprising: an anodeconsisting essentially of lithium or a lithium alloy; a cathode coatedonto a solid current collector, said cathode coating comprising irondisulfide as an active material; a high temperature polymeric separatorcomprising a polymer having a melting point; an electrolyte having asolubility parameter; wherein the anode, the cathode and the separatorare spirally wound; and wherein, when the cell is discharged at a rateof 0.01 C or less and a temperature of 70° C. or greater, the solubilityparameter of the electrolyte is large enough relative to the meltingpoint of the polymer to prevent premature voltage dropoff.
 2. The cellaccording to claim 1, wherein the separator comprises polyimide.
 3. Thecell according to claim 2, wherein the separator is a bi-layer furthercomprising polyethylene.
 4. The cell according to claim 3, wherein thepolyimide is less than 30 microns, the polyethylene is greater than 10microns and a total thickness for the bi-layer separator is less than 50microns.
 5. An electrochemical cell comprising: an anode consistingessentially of lithium or a lithium alloy; a cathode coated onto a solidcurrent collector, said cathode coating comprising iron disulfide as anactive material; a high temperature polymeric separator having ascaffold structure comprising a first polymer and filling polymercomprising a second polymer; a liquid electrolyte that is distinct fromthe separator; wherein the anode, the cathode and the separator arespirally wound; wherein the liquid electrolyte is at least partiallyabsorbed by the second polymer; and wherein the first polymer does notsoften at an expected discharge temperature for the cell.
 6. The cellaccording to claim 5, wherein the first polymer comprises polyimide andthe expected discharge temperature is at least 90° C.